US3607794A - Process of reaction organic polyisocyanate with alkali metal silicate solution - Google Patents

Process of reaction organic polyisocyanate with alkali metal silicate solution Download PDF

Info

Publication number
US3607794A
US3607794A US726553A US3607794DA US3607794A US 3607794 A US3607794 A US 3607794A US 726553 A US726553 A US 726553A US 3607794D A US3607794D A US 3607794DA US 3607794 A US3607794 A US 3607794A
Authority
US
United States
Prior art keywords
silicate
process according
reaction
alkali metal
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US726553A
Other languages
English (en)
Inventor
William Abbotson
John Miles Macnair
Frederick James Wallace
Peter John Hancox
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Conteki Development Ltd
Original Assignee
Conteki Development Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Conteki Development Ltd filed Critical Conteki Development Ltd
Application granted granted Critical
Publication of US3607794A publication Critical patent/US3607794A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/003—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hybrid binders other than those of the polycarboxylate type
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/302—Water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
    • C08G18/3895—Inorganic compounds, e.g. aqueous alkalimetalsilicate solutions; Organic derivatives thereof containing no direct silicon-carbon bonds

Definitions

  • Siliceous products may be made by direct reaction between an alkali metal silicate and an organic isocyanate or isothiocyanate. By varying the proportions, reaction conditions and ingredients used, products varying from light cellular foams, to mastics and high-density solids may be obtained.
  • This invention relates to the production of siliceous products, to products containing a body of siliceous material and to the uses of such products.
  • a process for the production of siliceous products which comprises reacting an aqueous solution of an alkali metal silicate with an organic isocyanate or isothiocyanate, preferably an organic polyisocyanate.
  • an organic isocyanate or isothiocyanate preferably an organic polyisocyanate.
  • reaction referred to causes the alkali metal silicate solution to set and, whilst the applicants would not wish to be bound by any theory as to why this occurs, it is considered probable that a number of chemical reactions are involved.
  • organic polyisocyanates and water react together with the production of polymers of which the structural units are linked together by urea linkages.
  • a byproduct of that reaction is carbon dioxide. It is am almost certain that at least part of the reaction is the production of carbon dioxide and the reaction is the production of carbon dioxide and the reaction of that carbon dioxide with the alkali metal silicate to form a solid silica hydrogel. From the general appearance of the cellular compositions, however, there would appear to be some polymerization occuring which is not explained by the inorganic reactions.
  • the polymer structure may be due to the formation of polyureas or polymerization of the isocyanate into complex isocyanate and/or isocyanurate compounds.
  • An alternate explanation would be the formation of a silicon chain structure through the hydroxyl groups of the silicate reacting with the isocyanate.
  • Suitable polyisocyanates which be employed in the process of the invention are exemplified by the organic diisocyanates which are compounds of the general formula:
  • R is a divalent organic radical such as an alkylene, aralkylene or arylene radical. Suitable such radicals may contain, for example, 2 to carbon atoms.
  • polyisocyanates polyisothiocyanates and their derivatives may be equally employed.
  • Fatty diisocyanates are also suitable of the general formula ITIC 0 (CH2) 1 OH3(C 2)X 2)y where x+y totals 6 to 22 and z is 0 to 2, e.g. isocyanatostearyl isocyanate.
  • ITIC 0 (CH2) 1 OH3(C 2)X 2)y where x+y totals 6 to 22 and z is 0 to 2
  • p,p'-diphenylmethane diisocyanate has been found in practice to be most suitable.
  • Tolylene diisocyanates eg the 2,4- and 2,6-isomers, are also readily available and suitable for use.
  • aqueous alkali metal silicates have been found to give satisfactory results.
  • Such silicates can be represented as M 0. SiO, where M represents an atom of an alkali metal and they differ in the ratio of M O'SiO [t has been found that the sodium silicates are highly satisfactory and while the other alkali metal silicates, e.g. potassium and lithium silicates may be used they are less preferable on economic grounds.
  • the Na O:SiO ratio may vary, for example from 1.6: 1.0 to 3.3: l .0. However it is found generally to be preferable to employ a silicate of which the said ratio is within the range 20:10 to 2.3;1.0.
  • the relative proportions of the alkali metal silicate and the isocyanate may be varied yielding, as noted above, products of different physical characteristics and probably differing chemical structure.
  • the weight ratio of silicate to isocyanate may vary from 1:7.75 to 3:1. Within this range the general effect is that at the higher ratios of isocyanate the reaction proceeds very rapidly and the products tend to be of low density whereas at the high ratios of silicate the reaction produces products of higher density.
  • tertiary amines serving as accelerators are, for example, trialkylamines, e.g.
  • dialkylalkanolamines and alkyl dialkanolamines such as N,N-dialkyl ethanolamines such as triethanolamines, pyrimidine, quinoline, dimethylaniline, N-alkylmorpholines, NzN-dimethyl cyclohexylamine, NzN-dimethyl benzylamine and triethylene diamine.
  • Other compounds having a catalytic or accelerative activity may be used, examples being lead benzoate and oleate, stannic chloride, stannous octoate, lead octoate, bismuth nitrate, antimony trichloride and dibutyl tin dilaurate. Or a mixture of said tertiary amine and a said salt may be used.
  • the particular physical condition of the final product depends on the particular agents used and their relative proportions. Thus it has been found that if the conditions are adjusted to afford the evolution of a considerable volume of carbon dioxide gas, a foaming of the reaction mixture takes place so that the products set to a highly cellular condition. if desired, the foaming may be assisted by the use of a blowing agent known per se included in the composition, e.g. a volatile fluorinated hydrocarbon such as are sold under the Registered Trade Marks FREON and ARCTON, as for instance, trichlorofluoromethane, or a substance such as azoisobutyronitrile.
  • a blowing agent known per se included in the composition, e.g. a volatile fluorinated hydrocarbon such as are sold under the Registered Trade Marks FREON and ARCTON, as for instance, trichlorofluoromethane, or a substance such as azoisobutyronitrile.
  • the cellular products of the present invention since they are of low density and high thermal and sound insulating value, are of particular importance. In their production it is convenient to include in the reaction mixture an agent which will held to stabilize or strengthen the cellular structure and render it more uniform.
  • a surfactant This may be anionic, cationic or nonionic and a wide variety of such surfactant compounds are available in commerce and may be used, e.g. long chain alkyl sulfates, alkyl benzene sulfonates, alkyl naphthalene sulphonates, and like anionic agents, cetyltrimethyl ammonium salts and like cationic agents and the ethylene oxide condensates per se or with phenols or amines and like nonionic agents. It has been found in practice that the nonionic agents are generally to be preferred. Silicones, i.e. polysiloxanes, also serve as useful foam stabilizing agents.
  • the reaction characteristic of the process of the invention is preferably carried out at ambient temperatures, e.g. to 25 C. Higher temperatures tend to accelerate the reaction but may make it more difficult to control.
  • the reaction mixture there may advantageously be present in the reaction mixture, as indicated above, in addition to the isocyanate and the silicate, an accelerator or catalyst for the reaction, a foaming agent and a foam stabilizing agent.
  • an accelerator or catalyst for the reaction in addition to the isocyanate and the silicate, an accelerator or catalyst for the reaction, a foaming agent and a foam stabilizing agent.
  • a foaming agent in addition to the isocyanate and the silicate, an accelerator or catalyst for the reaction, a foaming agent and a foam stabilizing agent.
  • the ratios of the main ingredients, isocyanate and silicate, to be additives should be approximately the following:
  • additives known per se to take part in the isocyanate polymer-forming reaction e.g. polyols such as hexane triol.
  • the characteristics of the products may be usefully modified by the inclusion of preformed polymers such as polyvinyl acetate, the copolymers of vinyl acetate and acrylic acid or methyl acrylate or methyl methacrylate, and copolymers of styrene with acrylic acid, methyl acrylate, methyl methacrylate or other ethylenically unsaturated monomers.
  • preformed polymers such as polyvinyl acetate, the copolymers of vinyl acetate and acrylic acid or methyl acrylate or methyl methacrylate, and copolymers of styrene with acrylic acid, methyl acrylate, methyl methacrylate or other ethylenically unsaturated monomers.
  • the said polymers may contain some residual hydroxyl groups which react with the isocyanate.
  • Wholly hydrocarbon polymers such as polyethylene are generally less effective additives.
  • a particular useful aspect of the invention derives from the inclusion in the reaction mixture of inert solid substances which, by reason of the reaction are thus distributed in the solid matrix of the end product.
  • the invention may be applied to the production of rigid products in which the alkali metal silicate solution constitutes a precursor for a binding agent for a filler material, Le. is converted by the process of this invention to a rigid matrix binding the particles together.
  • the filler materials may be organic or inorganic, fibrous or particulate, or mixtures of any of these, such as sand, alumina, aluminosilicates, magnesia, and other particulate refractories; metal fibers, asbestos, glass fiber, rock wool, aluminosilicate, calcium silicate fibers and other fibrous refractories; wood flour, coke and other organic or carbonaceous particles; paper pulp, cotton waste, cotton, jute, sisal, hemp, flax, rayon, or synthetic fibers such as polyester, polyamide and acrylonitrile fibers and other organic fibrous materials.
  • sand, alumina, aluminosilicates, magnesia, and other particulate refractories metal fibers, asbestos, glass fiber, rock wool, aluminosilicate, calcium silicate fibers and other fibrous refractories
  • wood flour, coke and other organic or carbonaceous particles paper pulp, cotton waste, cotton, jute,
  • the process is of special value in the production of heat-insulating shaped products for use in the metallurgical industry, e.g. in the foundry industry to constitute the binding system in sand mould and core-making operations or to constitute linings in the feedhead and risers of metal casting moulds.
  • the particulate material may comprise ingredients which react together exothermically when ignited, e.g. aluminothermic compositions, which are useful in the production of linings as aforesaid.
  • the particulate materials may be, for example, a mixture of finely divided aluminum, oxidizing agent therefor (e.g. a nitrate or chlorate, or iron oxide or manganese dioxide) along or together with particulate refractory material as aforesaid.
  • oxidizing agent e.g. a nitrate or chlorate, or iron oxide or manganese dioxide
  • the quantity of oxidizing agent should be stoichiometrically insufficient to react with all the aluminum present and that the composition should contain a small proportion of a fluoride, e.g. cryolite, aluminum fluoride or a complex fluoride such as fluoborate, fluotitanate or fluosilicate.
  • Cellular products made according to the present invention are not always sufficiently resistant to penetration by molten metal to permit their successful use in the lining of hot tops, risers, or the like in foundry practice. Where this is the case it is desirable to provide that the surface which is to contact the molten metal is of nonfoamed structure.
  • the foamed material may be provided, for example, with a facing layer resistant to metal penetration and, in some cases, more refractory than the foamed insulator.
  • a facing layer resistant to metal penetration and, in some cases, more refractory than the foamed insulator.
  • Such a layer may consist of a particulate refractory material, e.g. core sand, silica flour, alumina, bonded with a binder such as core oil or furane resin.
  • a refractory layer is preferably 1.5-4 mm. thick, most preferably about 2.5 mm. thick.
  • Suitable refractory coatings which may be employed include one comprising particulate refractory material, up to 5 percent of a binder effective at room temperature, 0.5 to 5 percent of a binder effective at high temperature and 0.1 to l0 percent of a suspending agent usually dispersed in a liquid medium, preferably water and one comprising chromic oxide and an inorganic binding agent therefor, usually dispersed in a liquid medium, preferably water.
  • a suspending agent usually dispersed in a liquid medium, preferably water and one comprising chromic oxide and an inorganic binding agent therefor, usually dispersed in a liquid medium, preferably water.
  • An alternative method of securing a nonfoamed surface structure is partially to defoam the slab during manufacture. This may be effected, for example, by spraying a defoaming agent onto the mould walls. Suitable defoaming agents are hexanol and nonanol. The collapse of the foam at the surface gives, in the final slab, an integrally formed nonfoamed structured surface which is highly resistant to molten metal penetration.
  • the inner dimensions of the foamed insulator are generally controlled by inserting into the head box or mould head opening a former, generally made of cardboard.
  • Foamed insulator precurser is then brought into the space between the former and the mould or head box walls and there caused to foam and set to give solid refractory foamed heat-insulative material.
  • the foam-contacting walls of the former the foam may be defoamed on contact with the former walls, giving a nonfoamed surface to the insulating material after the cardboard former has been removed.
  • the cardboard former may bear a refractory coating as described above which will be transferred to the face of the foamed insulator when the insulator foams and sets, and from which the cardboard former may subsequently be stripped.
  • the products of the invention having a cellular structure are good thermal insulants and therefore have a wide application in the insulation industry.
  • insulants have been divided into two categories: organic for low-temperature application and inorganic for use in the high-temperature field.
  • the foam products of the present invention combine the properties of both types.
  • the process of the invention thus affords the possibility of obtaining compositions having a high inorganic content and cellular products thus produced are considerably less combustible than the more conventionally known foamed plastics materials such as polystyrene and polyurethane.
  • compositions of the present invention are either flame proof or at least self-extinguishing.
  • the relative noninfiammability of the products of this invention thus lends particular value to their use in constructional applications e.g. as fireand flame-resistant heat and sound-insulating boards; as sprayed compositions for anticondensation insulation and fire resistance; as packaging materials; for sealing rock faces to prevent oxidation and erosion in the mining industry.
  • the noncellular products may be used to great advantage as mastics or sealing compounds or as cements and bonding agents.
  • EXAMPLE 1 A composition was prepared from the following ingredients;
  • Amine Catalyst (a mixture of 4% by weight 3 parts of N-fl-hydroxyethyl based upon dimethylamine and 1 part of the isocyanate percent triethylene diamine) present.
  • EXAMPLE 2 Sodium silicate solution (as in example I p.p"diphenylmethane diisocyanate Silicone foam stabilizer (as in example I) Amine Catalyst (as in example i 20 parts by weight 40 parts by weight I part by weight 4% by weight of the isocyanate.
  • compositions according to example 1 are noninflammable foams and are mechanically stronger than those according to example 2. Very little smoke is produced when a flame is applied to such compositions.
  • compositions of example 2 are self-extinguishing but not entirely fireproof, and greater volumes of smoke are produced when contacted by flame. They are very good insulators but are mechanically weaker.
  • inorganic fibrous material e.g. l2 percent by weight of asbestos
  • flame-resistant materials known per se, e.g. phosphates.
  • EXAMPLE 3 The following composition was mixed in a core sand mixer:
  • the sand and silicate were first mixed together for 2 minutes, and mixing was continued for a further 2 minutes after the addition of the other ingredients.
  • the resulting mixture which had a bench life of about 10 minutes, was formed into sand moulds and cores. lron castings were made using these moulds and cores, using a pouring temperature of l,400 C. The moulds and cores performed well, but nevertheless were easily stripped from the resulting castings.
  • Fine silica sand Sodium silicate solution (as in example 1) I00 parts by weight 6 parts by weight EXAMPLE 5 Insulating boards of greatly increased mechanical strength were made by pouring the reaction mixture of example 4 into a slab mould, which had been loosely filled with glass fibers, closing the mould and allowing the mixture to foam through the fibers.
  • longfibered materials as in the so-called glass rovings, as the fibers may then be orientated readily into whichever plane (or planes) is required when packing the mould.
  • the degree of foaming of the products can be controlled by the quantity and nature of the surfactants, blowing agents, etc., which are used. In the following example a completely nonfoamed product is obtained.
  • EXAMPLE 6 Sodium silicate solution (as in example 1) Diisocyanate (as in example I) Armeen DM 16D (Alkyl dimethylumine in which the alkyl group is predominantly polymity).
  • EXAMPLE 7 Sodium silicate (as in example i) Silcocell 380 (as in example I) l3.l parts by weight 0.7 parts by weight T ble Qontinucd 4.8 parts by weight 0.25 parts by weight 72.5 parts by weight 2.05 parts by weight 6.6 parts by weight The mixture was then poured into slab moulds measuring internally 9inches X 9inches X Zinches, one large face of which was constituted by a mm. thick plate of silicate-bonded sand (fine silica sand bonded with 6 percent by weight sodium silicate solution and dried).
  • the tiles were stripped from the moulds, after the reaction was complete, as duplex bodies having a dense (2 gJcc.) facing of silicate-bonded sand and a 2 inch thick, low density (0.51 g./cc.), heat insulating backing. They were used to line the heads of ingot moulds, the dense surface facing towards the interior of the mould to contact the molten metal when the moulds were filled.
  • a process for the production of a silica-containing refractory product which consists essentially of reacting together an aqueous solution of an alkali metal silicate and an organic polyisocyanate in the presence of an inert material selected from the group consisting of particulate materials, fibrous and mixtures thereof and in the absence of a preformed resin. 7
  • polyisocyanate is selected from the group consisting of p,p'-diphenylmethane diisocyanate and tolylene diisocyanate.
  • alkali metal silicate is sodium silicate of which the Na zSi0 ratio of the sodium silicate is within the range of about 1.621 to about 3.311.
  • silicate is sodium silicate with a Na flzsifl ratio in the range of about 2.0:! to about 2,311
  • the isocyanate is p,p'-diphenylmethane diisocyanate having about a percent purity and the weight of ratio of silicate to isocyanate is in the range of about 1:7.75 to about 3:1.
  • particulate and fibrous materials are refractory materials.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US726553A 1967-05-12 1968-05-03 Process of reaction organic polyisocyanate with alkali metal silicate solution Expired - Lifetime US3607794A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB2219067 1967-05-12
GB34884/67A GB1186771A (en) 1967-05-12 1967-05-12 Silicious Products

Publications (1)

Publication Number Publication Date
US3607794A true US3607794A (en) 1971-09-21

Family

ID=26255781

Family Applications (1)

Application Number Title Priority Date Filing Date
US726553A Expired - Lifetime US3607794A (en) 1967-05-12 1968-05-03 Process of reaction organic polyisocyanate with alkali metal silicate solution

Country Status (8)

Country Link
US (1) US3607794A (enrdf_load_stackoverflow)
BE (1) BE715016A (enrdf_load_stackoverflow)
DE (1) DE1770384A1 (enrdf_load_stackoverflow)
ES (1) ES353810A1 (enrdf_load_stackoverflow)
FR (1) FR1564346A (enrdf_load_stackoverflow)
GB (1) GB1186771A (enrdf_load_stackoverflow)
IL (1) IL29900A0 (enrdf_load_stackoverflow)
NL (1) NL166002C (enrdf_load_stackoverflow)

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3891594A (en) * 1972-04-07 1975-06-24 Lynn J Taylor Direct synthesis of composite materials
US3960805A (en) * 1974-04-19 1976-06-01 Lynn Johnston Taylor Direct synthesis of organic polymer-inorganic oxide composites
US3975316A (en) * 1972-05-04 1976-08-17 Thiokol Corporation Curing liquid polyurethane prepolymers
US3981831A (en) * 1973-11-30 1976-09-21 Bayer Aktiengesellschaft Inorganic-organic plastic
US3983081A (en) * 1973-02-02 1976-09-28 Bayer Aktiengesellschaft Inorganic-organic composition
US4005035A (en) * 1974-12-24 1977-01-25 Tecnik International Corporation Composition for reinforced and filled high density rigid polyurethane foam products and method of making same
US4042536A (en) * 1973-11-30 1977-08-16 Bayer Aktiengesellschaft Inorganic-organic plastic
US4052347A (en) * 1973-05-17 1977-10-04 Bayer Aktiengesellschaft Inorganic-organic compositions
US4097423A (en) * 1972-06-03 1978-06-27 Bayer Aktiengesellschaft Inorganic-organic compositions
US4108807A (en) * 1975-07-18 1978-08-22 Chemic-Anlagenbau Bischofsheim Gmbh Organo-metallate polymers and processes for the manufacture thereof
US4129696A (en) * 1975-03-20 1978-12-12 Bayer Aktiengesellschaft Process for the production of inorganic-organic plastic composites
US4136238A (en) * 1974-12-21 1979-01-23 Metallgesellschaft A.G. Non-flammable and optionally electrically conductive organo-silicate polymers and process for preparing same
US4142030A (en) * 1973-11-30 1979-02-27 Bayer Aktiengesellschaft Inorganic-organic plastic
DE2908746A1 (de) * 1979-03-06 1980-09-18 Bayer Ag Verfahren zum verfestigen und abdichten von geologischen und geschuetteten gesteins- und erdformationen
WO1981002300A1 (en) * 1980-02-04 1981-08-20 D Blount Production of poly(polyisocyanate silicate)solid or cellular solid utilizing alkali metal silicates
WO1982002388A1 (en) * 1980-12-30 1982-07-22 David H Blount Process for the production of alkali metal polyester silicate resinous products
US4447561A (en) * 1982-07-23 1984-05-08 Basf Aktiengesellschaft Stable water glass solutions, process for their preparation and use for organosilicate foams as well as a production process therefor
USRE31946E (en) * 1979-03-06 1985-07-16 Bergwerksverband Gmbh Process for consolidating and sealing off geological and artificially deposited rock and earth formations
US4669919A (en) * 1984-06-06 1987-06-02 Kvt Kunststoffverfahrenstechnik Gmbh & Co. Process for consolidation and sealing coal and/or rock, soil and brick formations in mining, tunnelling and construction
US4827005A (en) * 1984-06-06 1989-05-02 Kvt Kunststoffverfahrenstechnik Gmbh & Co. Organomineral products, a process for their manufacture and their use
US4904522A (en) * 1988-07-26 1990-02-27 Mobay Corporation Process for the production of fiberglass mats
US5462699A (en) * 1993-04-02 1995-10-31 Fireblock International, Inc. Fire retardant materials and methods of use thereof
WO2001058975A1 (en) * 2000-02-08 2001-08-16 Fosroc International Limited Compositions for the manufacture of organo-mineral products, products obtained therefrom and their use
US20050096411A1 (en) * 2003-10-31 2005-05-05 Illinois Tool Works Inc. Polyurethane adhesive for masonry construction
US20060051595A1 (en) * 2003-05-15 2006-03-09 Huntsman International Llc Polyisocyanate-based adhesive formulation for use in sandwich panels
WO2010067126A1 (en) 2008-12-11 2010-06-17 Minova International Limited Silicate isocyanate
WO2011012415A1 (en) 2009-07-30 2011-02-03 Construction Research & Technology Gmbh Siliceous-based polyurea compositions
US8633269B2 (en) 2010-12-01 2014-01-21 Mattel, Inc. Play modeling dough
USD803326S1 (en) 2013-03-15 2017-11-21 Mattel, Inc. Toy projectile
WO2021224218A1 (fr) 2020-05-07 2021-11-11 A Weber Composition bicomposante pour la formation d'un materiau organo-mineral injectable ou pompable, procedes de scellement et utilisations associes

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2359610C3 (de) * 1973-11-30 1981-09-17 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung flexibler, organisch-anorganischer Verbundkunststoffe mit niedrigem Heizwert und verbessertem Brandverhalten
DE2359614A1 (de) * 1973-11-30 1975-06-05 Bayer Ag Sulfonsaeure- und/oder sulfonatgruppen aufweisende polyisocyanate
DE2359607C2 (de) * 1973-11-30 1982-12-09 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung eines anorganisch-organischen Verbundmaterials
DE2359609C2 (de) * 1973-11-30 1983-09-29 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Xerosol-Kunststoffen
DE2460834C2 (de) * 1974-12-21 1987-04-16 Chemie-Anlagenbau Bischofsheim GmbH, 4500 Osnabrück Verfahren zur Herstellung von Organomineralschäumen
DE2542288C2 (de) * 1975-09-23 1988-12-01 Chemie-Anlagenbau Bischofsheim GmbH, 4500 Osnabrück Verfahren zur Herstellung von nichtentflammbaren homogenen oder geschäumten mineralische Füllstoffe enthaltenden Kunststoffen
DE2559255C2 (de) * 1975-12-31 1985-03-28 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung anorganisch-organischer Kunststoffe
DE2728074A1 (de) * 1977-06-22 1979-01-11 Bayer Ag Verfahren zur herstellung von mineralfasermatten
DE2842582A1 (de) * 1978-09-29 1980-08-21 Bischofsheim Chemie Anlagen Verfahren zur herstellung von geschaeumten oder nicht geschaeumten massen
US5191012A (en) * 1991-03-28 1993-03-02 Miles Inc. Aqueous dispersions of encapsulated polyisocyanates
HU212033B (en) * 1991-06-03 1996-01-29 Polinvent Kft Process for producing synthetic resins with controllable time of gelation, based on polyisocyanate/polysilicic acid
US20230082937A1 (en) * 2020-02-28 2023-03-16 Zeon Corporation Composite particle for electrochemical device and method of producing the same, and electrode for electrochemical device and electrochemical device

Cited By (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3891594A (en) * 1972-04-07 1975-06-24 Lynn J Taylor Direct synthesis of composite materials
US3975316A (en) * 1972-05-04 1976-08-17 Thiokol Corporation Curing liquid polyurethane prepolymers
US4097423A (en) * 1972-06-03 1978-06-27 Bayer Aktiengesellschaft Inorganic-organic compositions
US3983081A (en) * 1973-02-02 1976-09-28 Bayer Aktiengesellschaft Inorganic-organic composition
US4052347A (en) * 1973-05-17 1977-10-04 Bayer Aktiengesellschaft Inorganic-organic compositions
US4042536A (en) * 1973-11-30 1977-08-16 Bayer Aktiengesellschaft Inorganic-organic plastic
US4142030A (en) * 1973-11-30 1979-02-27 Bayer Aktiengesellschaft Inorganic-organic plastic
US3981831A (en) * 1973-11-30 1976-09-21 Bayer Aktiengesellschaft Inorganic-organic plastic
US3960805A (en) * 1974-04-19 1976-06-01 Lynn Johnston Taylor Direct synthesis of organic polymer-inorganic oxide composites
US4136238A (en) * 1974-12-21 1979-01-23 Metallgesellschaft A.G. Non-flammable and optionally electrically conductive organo-silicate polymers and process for preparing same
US4005035A (en) * 1974-12-24 1977-01-25 Tecnik International Corporation Composition for reinforced and filled high density rigid polyurethane foam products and method of making same
US4129696A (en) * 1975-03-20 1978-12-12 Bayer Aktiengesellschaft Process for the production of inorganic-organic plastic composites
US4108807A (en) * 1975-07-18 1978-08-22 Chemic-Anlagenbau Bischofsheim Gmbh Organo-metallate polymers and processes for the manufacture thereof
DE2908746A1 (de) * 1979-03-06 1980-09-18 Bayer Ag Verfahren zum verfestigen und abdichten von geologischen und geschuetteten gesteins- und erdformationen
US4307980A (en) * 1979-03-06 1981-12-29 Bergwerksverband Gmbh Process for consolidating and sealing off geological and artificially deposited rock and earth formations
USRE31946E (en) * 1979-03-06 1985-07-16 Bergwerksverband Gmbh Process for consolidating and sealing off geological and artificially deposited rock and earth formations
WO1981002300A1 (en) * 1980-02-04 1981-08-20 D Blount Production of poly(polyisocyanate silicate)solid or cellular solid utilizing alkali metal silicates
WO1982002388A1 (en) * 1980-12-30 1982-07-22 David H Blount Process for the production of alkali metal polyester silicate resinous products
US4447561A (en) * 1982-07-23 1984-05-08 Basf Aktiengesellschaft Stable water glass solutions, process for their preparation and use for organosilicate foams as well as a production process therefor
US4827005A (en) * 1984-06-06 1989-05-02 Kvt Kunststoffverfahrenstechnik Gmbh & Co. Organomineral products, a process for their manufacture and their use
US4669919A (en) * 1984-06-06 1987-06-02 Kvt Kunststoffverfahrenstechnik Gmbh & Co. Process for consolidation and sealing coal and/or rock, soil and brick formations in mining, tunnelling and construction
US4871829A (en) * 1984-06-06 1989-10-03 Kvt Kunststoffverfahrenstechnik Gmbh & Co. Organomineral products, a process for their manufacture and their use
US4904522A (en) * 1988-07-26 1990-02-27 Mobay Corporation Process for the production of fiberglass mats
US5462699A (en) * 1993-04-02 1995-10-31 Fireblock International, Inc. Fire retardant materials and methods of use thereof
WO2001058975A1 (en) * 2000-02-08 2001-08-16 Fosroc International Limited Compositions for the manufacture of organo-mineral products, products obtained therefrom and their use
US20030139525A1 (en) * 2000-02-08 2003-07-24 Harald Bode Compositions for the manufacture of organo-mineral products, products obtained therefrom and their use
AU768384B2 (en) * 2000-02-08 2003-12-11 Minova International Limited Compositions for the manufacture of organo-mineral products, products obtained therefrom and their use
US6713554B2 (en) * 2000-02-08 2004-03-30 Fosroc International Limited Compositions for the manufacture of organo-mineral products, products obtained therefrom and their use
US20060051595A1 (en) * 2003-05-15 2006-03-09 Huntsman International Llc Polyisocyanate-based adhesive formulation for use in sandwich panels
US20050096411A1 (en) * 2003-10-31 2005-05-05 Illinois Tool Works Inc. Polyurethane adhesive for masonry construction
WO2010067126A1 (en) 2008-12-11 2010-06-17 Minova International Limited Silicate isocyanate
WO2011012415A1 (en) 2009-07-30 2011-02-03 Construction Research & Technology Gmbh Siliceous-based polyurea compositions
US8785539B2 (en) 2009-07-30 2014-07-22 Construction Research & Technology Gmbh Siliceous-based polyurea compositions
RU2547183C2 (ru) * 2009-07-30 2015-04-10 Констракшн Рисёрч & Текнолоджи Гмбх Полимочевинные композиции на кремниевой основе
US8633269B2 (en) 2010-12-01 2014-01-21 Mattel, Inc. Play modeling dough
US9193859B2 (en) 2010-12-01 2015-11-24 Mattel, Inc. Play modeling dough
USD803326S1 (en) 2013-03-15 2017-11-21 Mattel, Inc. Toy projectile
US9829290B2 (en) 2013-03-15 2017-11-28 Mattel, Inc. Toy projectile and method of making
WO2021224218A1 (fr) 2020-05-07 2021-11-11 A Weber Composition bicomposante pour la formation d'un materiau organo-mineral injectable ou pompable, procedes de scellement et utilisations associes
FR3109940A1 (fr) 2020-05-07 2021-11-12 A Weber Composition bicomposante pour la formation d’un matériau organo-minéral injectable ou pompable, procédés de scellement et utilisations associés
US20230183136A1 (en) * 2020-05-07 2023-06-15 Weber Mining & Tunnelling Two-component composition for forming an injectable or pumpable organo-mineral material, and associated sealing methods and uses

Also Published As

Publication number Publication date
GB1186771A (en) 1970-04-02
ES353810A1 (es) 1969-10-16
DE1770384A1 (de) 1971-10-14
NL166002C (nl) 1981-06-15
NL6806703A (enrdf_load_stackoverflow) 1968-11-13
FR1564346A (enrdf_load_stackoverflow) 1969-04-18
NL166002B (nl) 1981-01-15
IL29900A0 (en) 1968-08-22
BE715016A (enrdf_load_stackoverflow) 1968-09-30

Similar Documents

Publication Publication Date Title
US3607794A (en) Process of reaction organic polyisocyanate with alkali metal silicate solution
US3983081A (en) Inorganic-organic composition
CA1209738A (en) Polyurethane foams and processes for preparation
CA1063299A (en) Highly filled polyurea foams
US4097423A (en) Inorganic-organic compositions
US4097422A (en) Inorganic-organic compositions
US4724250A (en) One-component molding material and its use as construction material
US3951885A (en) Method of making magnesium oxychloride cement cofoamed with synthetic resin
JPH0335088A (ja) 耐燃性要素
US4082702A (en) Flame retardant rigid polyurethane syntactic foam
US4170697A (en) Process for the production of polyisocyanate silicate solid or cellular solid products
US4207113A (en) Inorganic foam and preparation thereof
CN108973268B (zh) 一种建筑保温硬面板及其制备方法
US4871829A (en) Organomineral products, a process for their manufacture and their use
US3766100A (en) Rigid phenolic foams suitable for use as non flammable insulating material
US4098730A (en) Non-flammable organo-red mud polymers, some of which are electrically conductive, and process for their manufacture
AT391466B (de) Anorganische thermoisolationsmasse
AT283180B (de) Verfahren zur Herstellung von kieselsäurehaltigen Produkten, insbesondere für Isolierzwecke
RU2184126C2 (ru) Связующее для теплоизоляционного материала и способ изготовления теплоизоляционного материала
US4242497A (en) Production of amino-silicate compounds, condensation resinous products
US4332926A (en) Process for the production of alkali metal silicate-organic plastics
US2803606A (en) Powdered siloxane resin and process of preparing cellular resin therefrom
DE2318167A1 (de) Verfahren zur herstellung von leichtbauelementen
CA1279139C (en) Intumescent fire retardant compositions
RU2079525C1 (ru) Композиция для получения огнезащитного материала и способ его получения